This subproject is one of many research subprojects utilizing the resources provided by a Center grant funded by NIH/NCRR. Primary support for the subproject and the subproject's principal investigator may have been provided by other sources, including other NIH sources. The Total Cost listed for the subproject likely represents the estimated amount of Center infrastructure utilized by the subproject, not direct funding provided by the NCRR grant to the subproject or subproject staff. Because electrochemistry allows one to selectively manipulate the oxidation state of molecules, create reactive intermediates, and reverse the polarity of known functional groups, it provides and ideal method for discovering and exploring many new, synthetically useful reactions. For example, we have found that the anodic oxidation of electron-rich olefins leads to the formation of radical cations that efficiently trap nucleophiles. In this way, normally nucleophilic enolate equivalents can be used as electrophiles. Current efforts to exploit this unique umpolung reaction are focusing on the construction of natural products. In a similar fashion, we are taking advantage electrochemistry's ability to reverse the normal polarity of N-acyliminium ion formation in order to develop new approaches to diversity-oriented synthesis that allow for systematic variations within a core scaffold to synthesize receptor-targeted molecular libraries that contain conformational probes for rapidly gathering information about the three dimensional requirements of the receptor, and to construct new peptide-based bioconjugates.